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The review discusses the latest advances in the directed synthesis and application of macroheterocyclic compounds in science, engineering and technology, viz. as catalysts for various processes in photo- and electrocatalysis, optical chemosensors for metal cations, selective receptors of organic compounds, inductors and selectors, in nonlinear optics, organic electronics, as magnets, photosensitizers for PDT of a number of oncological diseases and for antimicrobial PDT, etc.

Statistical condensation of 4’,5’-dicyanobenzo-15-crown-5 and 4,5-dibutoxyphthalonitrile in the presence of Mg2+ as a template led to a mixture of complexes, which was separated to isolate mono-crown-substituted magnesium phthalocyaninate Mg[(15C5)(BuO)6Pc]. Its demetallation afforded corresponding metal-free ligand, H2[(15C5)(BuO)6Pc]. Aggregation of this phthalocyanine was studied both in concentrated solutions (up to 1.32·10-3 M in chloroform), or in the presence of potassium acetate. Application of nonlinear regression for analysis of spectrophotometric data provided evidences of dimerization of phthalocyanine molecules under these conditions. Architecture of dimers is discussed.

A convenient synthetic approach towards alkyloxy substituted (24-crown-8)-linked dimeric phthalocyanines is developed. The influence of the alteration of the reaction conditions and the origin of the precursors onto the yield of the target compounds is revealed. The Mg-templated statistical condensation of the mixture of phthalonitriles is found to be the most efficient and versatile pathway. The developed demetallation procedure of obtained Mg-phthalocyanines allows to prepare metal-free (24-crown-8)-linked dimeric phthalocyanines, which are versatile precursors for preparation of other metal complexes. The preliminary AM1 semi-empirical calculations have demonstrated that the dimeric linked phthalocyanine metal complexes may become convenient receptors for recognition of ditopic guests.

This brief review summarizes the synthetic approaches towards porphyrins bearing a C-P bond at the periphery of the macrocycle. In the first section we detail the non catalytic pathways for the synthesis of phosphorus substituted porphyrins using different phosphonate precursors or by derivatization of a pre-existing porphyrin. In the second section we demonstrate that palladium- or copper-catalyzed phosphorylation of halogen substituted porphyrins is an efficient method to prepare meso- and β-phosphoryl substituted porphyrins.

The effective synthesis of Pd(II) monofunctional azomethine derivatives of coproporphyrin isomers I and II is reported. The proposed method is based on the interaction of a “phosphorus complex”, generated in situ by Vilsmeier-Haack reaction, with various amines. The reaction with palladium complex of coproporphyrin II gave Schiff bases as a mixture of two structural isomers in 4:1 ratio. The structure of the obtained compounds was determined using 1H, 13C, 1H-1H NOESY and UV-vis spectroscopy and mass spectrometry data.

Series of substituted phthalonitriles (4,5-bis[2'-(2''-benzyloxyethoxy)ethoxy]phthalonitrile, 4,5-bis(2-ethoxyethoxy) phthalonitrile and 4',5',4'',5''-tetracyanodibenzo-24-crown-8) was obtained by means of Pd-catalyzed cyanation reaction in high yields. Analysis of the obtained results together with previously reported data concerning transition metal catalyzed synthesis of phthalonitriles and analogues reveals advantages of each of these methods in comparison with classical approaches - ammonolysis/dehydratation and Rosenmund-Braun cyanation.

Продолжено изучение возможности растворения окта-[(4’-бензо-15-краун-5)окси]фталоцианинов (Mcr8Pc) в полярных растворителях с диэлектрической проницаемостью >30. На примере Cocr8Pc показано, что его растворимость в ряду диметилформамид – диметилсульфоксид – пропиленкарбонат – вода как в индивидуальных растворителях, так и в присутствии фоновых солей определяется сложным сочетанием нековалентных взаимодействий фталоцианин-фталоцианин и фталоцианин-среда. Методами электронной спектроскопии поглощения и рентгеновского малоуглового рассеяния исследовано влияние центрального иона Pc красителя на поведение Mcr8Pc в водных растворах солей калия. Установлено, что все свежеприготовленные растворы (Mcr8Pc, M = H2, Zn, Mg) с концентрацией ~10-4 М наряду с раствором содержат твердые частицы (~ 25 нм), причем наиболее инертным оказался Mgcr8Pc. Высказано предположение, что это связано с наличием кристаллической фазы в этом соединении. Показано, что для получения растворов необходима выдержка более двух недель.

aFrumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, 199071 Moscow, Russia bLomonosov Moscow University of Fine Chemical Technology, 119571 Moscow, Russia cOrekhovich Institute of Biomedical Chemistry of Russian Academy of Medical Sciences, 119832 Moscow, Russia dIvanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia @Corresponding author E-mail: joz@mail.ru

Исследована адсорбция свободного гемоглобина из плазмы крови на активированном угле СКТ-6А, модифицированном аффинными агентами. «Мягкие» ионы Cu2+ были электрохимически иммобилизованы на поверхности угля, «мягкий» лиганд йодид ион Iвходил в качестве допанта в состав полипиррола (ПП), электрохимически нанесенного на поверхность угля. Обнаружено, что скорость адсорбции свободного гемоглобина значительно уменьшается в плазме крови по сравнению с адсорбцией из водных растворов при использовании в качестве аффинного агента ионов Cu2+, тогда как аффинные свойства йодида иона Iпо отношению к свободному гемоглобину остаются неизменными. Были предложены различные механизмы взаимодействия молекулы гемоглобина с указанными аффинными агентами. Впервые синтезирован аффинный агент в виде аниона, допированного в структуру электропроводного полимера, и выявлена его активность по отношению к молекуле свободного гемоглобина.

Physico-chemical properties of monolayers of tetra-15-crown-5-phthalocyanine ligand were studied using LangmuirBlodgett technique and fiber optic spectroscopy. Dependences between concentration of monolayer forming solution and phthalocyanine ligand aggregation degree in monolayer were established. True stable monolayers of tetra-15crown-5-phthalocyanine ligand at the air/water interface were formed with orientation of phthalocyanine macrocycle planes parallel to the subphase surface. It was proven that absence of aggregates in solution does not guarantee absence of aggregation in the monolayer upon its formation. It was shown that studied substance generates columnar aggregates upon compression even in monolayer formed from extremely diluted solutions. Using special IR-spectroscopy techniques, it was shown that orientation of molecules relative to the substrate surface remains the same upon formation of solid ultrathin films by Langmuir-Blodgett technique.